Fluorination Enables Dual Ferroelectricity in Both Solid- and Liquid-Crystal Phases

[Image: see text] Ferroelectric materials are a special type of polar substances, including solids or liquid crystals. However, obtaining a material to be ferroelectric in both its solid crystal (SC) and liquid crystal (LC) phases is a great challenge. Moreover, although cholesteric LCs inherently possess the advantage of high fluidity, their ferroelectricity remains unknown. Here, through the reasonable H/F substitution on the fourth position of the phenyl group of the parent nonferroelectric dihydrocholesteryl benzoate, we designed ferroelectric dihydrocholesteryl 4-fluorobenzoate (4-F-BDC), which shows ferroelectricity in both SC and cholesteric LC phases. The fluorination induces a lower symmetric polar P1 space group and a new solid-to-solid phase transition in 4-F-BDC. Beneficial from fluorination, the SC and cholesteric LC phases of 4-F-BDC show clear ferroelectricity, as confirmed by well-shaped polarization–voltage hysteresis loops. The dual ferroelectricity in both SC and cholesteric LC phases of a single material was rarely found. This work offers a viable case for the exploration of the interplay between ferroelectric SC and LC phases and provides an efficient approach for designing ferroelectrics with dual ferroelectricity and cholesteric ferroelectric liquid crystals.